CN112028408B - Advanced treatment method and system for aromatic and heterocyclic compound wastewater - Google Patents
Advanced treatment method and system for aromatic and heterocyclic compound wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 112
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 33
- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 82
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 73
- 230000003647 oxidation Effects 0.000 claims abstract description 57
- 238000005189 flocculation Methods 0.000 claims abstract description 38
- 230000016615 flocculation Effects 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000020477 pH reduction Effects 0.000 claims abstract description 21
- 230000007062 hydrolysis Effects 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000004062 sedimentation Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000002808 molecular sieve Substances 0.000 claims description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 32
- 230000001590 oxidative effect Effects 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000013459 approach Methods 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 description 12
- 231100000719 pollutant Toxicity 0.000 description 12
- 239000010865 sewage Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 7
- 230000001988 toxicity Effects 0.000 description 7
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 3
- 231100000086 high toxicity Toxicity 0.000 description 3
- OHDYZVVLNPXKDX-UHFFFAOYSA-N 2,3-dichlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1Cl OHDYZVVLNPXKDX-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VMHZXXPDUOVTHD-UHFFFAOYSA-N 2,3,4-trichloropyridine Chemical compound ClC1=CC=NC(Cl)=C1Cl VMHZXXPDUOVTHD-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- UGEJOEBBMPOJMT-UHFFFAOYSA-N 3-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(C(F)(F)F)=C1 UGEJOEBBMPOJMT-UHFFFAOYSA-N 0.000 description 1
- -1 Benzotrifluoride (TFA) Chemical compound 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
Abstract
The invention discloses a method and a system for advanced treatment of aromatic and heterocyclic compound wastewater. The system comprises a primary oxidation flocculation tank, a sedimentation tank, a primary ozone catalytic reaction tank, an MBR biochemical treatment system, a secondary ozone catalytic reaction tank and a secondary oxidation flocculation tank which are sequentially connected, wherein the MBR biochemical treatment system comprises a hydrolysis acidification tank, an A/O tank, an MBR membrane tank and an MBR water producing tank which are sequentially connected, the hydrolysis acidification tank is connected with the primary ozone catalytic reaction tank, and the MBR water producing tank is connected with the secondary ozone catalytic reaction tank. The treatment system can thoroughly remove high-concentration aromatic and heterocyclic compounds in the raw water of the wastewater, and the effluent completely reaches the existing emission standard, even approaches to the reuse standard.
Description
Technical Field
The invention relates to the technical field of pollutant treatment, in particular to an advanced treatment method and an advanced treatment system for aromatic and heterocyclic compound wastewater.
Background
At present, aiming at the treatment of the organic wastewater difficult to degrade, the most adopted method is a high-grade oxidation method, namely, hydroxyl free radicals with strong oxidability are generated through various oxidants or external energy sources (light energy, electric energy and the like), and macromolecular pollutants are mineralized into micromolecular pollutants or CO 2 Thereby reducing the COD concentration of the wastewater. However, for refractory organic substances, especially for various aromatic compounds and heterocyclic compounds (furan, pyridine, etc.), the degradation efficiency is limited, and in the process of destroying the structure, the generated small molecular compounds have large concentration and complex types, which leads to the COD of the wastewater not decreasing and rising in a certain period of time, thus the reaction time is prolonged continuously, and then oxygen is led toThe dosage and the energy consumption of the chemical agent are obviously increased. In addition, wastewater containing aromatic and heterocyclic compounds has high toxicity, and if the wastewater cannot be completely degraded, even if the effluent reaches the first-level B standard (COD is less than 60 mg/L), undegraded residual compounds in the wastewater still cause serious harm to the environment and organisms. On the other hand, with the single advanced oxidation system, the reaction speed is continuously reduced along with the extension of the reaction time, the removal rate of pollutants also tends to be stable, and the advanced treatment is difficult to realize. Therefore, development of more efficient degradation technology is required to thoroughly degrade such hardly degradable organic wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a deep treatment system for aromatic and heterocyclic compound wastewater, through which high-concentration aromatic and heterocyclic compounds in the wastewater can be effectively removed, and effluent completely reaches the existing emission standard, even approaches to the recycling standard.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the advanced treatment system for the aromatic and heterocyclic compound wastewater comprises a primary oxidation flocculation tank, a sedimentation tank, a primary ozone catalytic reaction tank, an MBR biochemical treatment system, a secondary ozone catalytic reaction tank, a secondary oxidation flocculation tank and an electrocatalytic reaction tank which are sequentially connected, wherein the MBR biochemical treatment system comprises a hydrolysis acidification tank, an A/O tank, an MBR membrane tank and an MBR water producing tank which are sequentially connected, the hydrolysis acidification tank is connected with the primary ozone catalytic reaction tank, and the MBR water producing tank is connected with the secondary ozone catalytic reaction tank.
Compared with the conventional wastewater treatment system, the invention is additionally provided with the primary oxidation flocculation tank, the sedimentation tank and the primary ozone catalytic reaction tank before the MBR biochemical treatment system, so that the COD value of the wastewater and the toxicity of the wastewater are reduced as much as possible, and the stable and efficient operation of the subsequent MBR biochemical treatment system is ensured. The invention adds a secondary ozone catalytic reaction tank and a secondary oxidation flocculation tank at the rear end of the MBR biochemical treatment system as a two-stage advanced oxidation treatment system, and further degrades residual pollutants in the MBR produced water, so that the effluent reaches the emission standard. The system is suitable for the existing sewage treatment plants, especially the enterprise pretreatment sewage treatment plants of fine chemical industry, and the reconstruction and extension of the centralized sewage treatment plants in the park.
Further, the advanced treatment system of the aromatic and heterocyclic compound wastewater further comprises an electrocatalytic reaction tank, and the electrocatalytic reaction tank is connected with the secondary oxidation flocculation tank.
In order to ensure that the effluent quality meets the standard and no high-toxicity pollutant exists in the water body (taking GC or HPLC as a standard, which is not detected), the invention also adds an electrocatalytic reaction tank at the rear end of the two-stage advanced oxidation treatment system, when the effluent of the two-stage oxidation flocculation tank still does not meet the standard, the electrocatalytic reaction tank can be started to carry out the final advanced degradation, and the residual organic pollutant of the wastewater is thoroughly removed by an electrolysis method, so that the effluent meets the emission standard and even approaches the reuse standard.
Further, the electrocatalytic reaction tank contains 4-8 electrode plates, and residual substances in the wastewater are thoroughly degraded under the electrolytic action of the multidimensional electrode.
Further, the first-stage ozone catalytic reaction tank and the second-stage ozone catalytic reaction tank both contain ZSM-5 type molecular sieves, which is beneficial to improving the contact area of ozone and water, so that organic pollutants in wastewater fully react with ozone, the treatment depth of the organic wastewater is improved, and the COD value of the wastewater is reduced.
The invention also provides a deep treatment method of the aromatic and heterocyclic compound wastewater, which comprises the following steps:
(1) The wastewater undergoes primary oxidation reaction and flocculation precipitation in a primary oxidation reaction flocculation tank added with an oxidant and a flocculant, and enters a sedimentation tank for solid-liquid separation;
(2) The wastewater after flocculation precipitation enters a primary ozone catalytic reaction tank to carry out primary ozone catalytic reaction;
(3) The wastewater after the reaction in the step (2) enters an MBR biochemical treatment system for biochemical treatment;
(4) The wastewater after biochemical treatment is subjected to a secondary ozone catalytic reaction in a secondary ozone catalytic reaction tank, and then enters a secondary oxidation flocculation tank to carry out a secondary oxidation reaction.
Because of the stable structure of the aromatic and heterocyclic compounds, conventional advanced oxidation techniques are difficult to achieve deep thorough oxidation. The invention adopts the process of 'primary oxidation + primary ozone catalysis + hydrolytic acidification + MBR + secondary ozone catalysis + secondary oxidation', can remove high-concentration aromatic and heterocyclic compounds in the wastewater, and the effluent not only completely reaches the existing emission standard, but also approaches the reuse standard.
Further, in the step (1), the adding amount of the oxidant is 0.3-0.4% of the total mass of the wastewater, the oxidant is hydrogen peroxide with the concentration of 25wt%, and the reaction time is 20-25min, so that the COD value of the wastewater is reduced.
Further, in the step (2), the ozone is added in an amount of 2-4mg O 3 COD mg, ozone mass concentration of 75% -80%, reaction time of 15-20min;
the ZSM-5 type molecular sieve is added in the first-stage ozone catalytic reaction, the adding amount of the ZSM-5 type molecular sieve is 1.2% -1.6% of the total mass of the wastewater, and the particle size of the ZSM-5 type molecular sieve is 20-30 meshes;
in the process parameter range, the COD value of the wastewater is reduced, the toxicity of the inflow water of the MBR biochemical treatment system is degraded, and the biodegradability of the inflow water is improved.
Further, in the step (4), the ozone adding amount in the secondary ozone catalytic reaction is 1.5-2.5mg O 3 COD mg, ozone mass concentration of 55% -60%, reaction time of 15-20min;
ZSM-5 type molecular sieve is added in the secondary ozone catalytic reaction, the adding amount of the ZSM-5 type molecular sieve is 1% -1.4% of the total mass of the wastewater, and the particle size of the ZSM-5 type molecular sieve is 20-30 meshes;
the adding amount of the oxidant in the secondary oxidation reaction is 0.1-0.2% of the total mass of the wastewater, and the oxidant is H with the mass concentration of 16-20% 2 O 2 The reaction time is 10-15min.
Within these process parameters, further degradation of the residual organics is favored.
Further, the advanced treatment method of the aromatic and heterocyclic compound wastewater further comprises the following steps:
(5) And (3) the wastewater subjected to the oxidation treatment in the step (4) enters an electrocatalytic reaction tank for electrocatalytic oxidation reaction. When the effluent of the secondary oxidation flocculation tank still does not reach the standard, in order to further ensure that the quality of the effluent reaches the standard, the electrocatalytic reaction tank can be started to carry out final deep degradation, and the process of primary oxidation, primary ozone catalysis, hydrolytic acidification, MBR, secondary ozone catalysis, secondary oxidation and electrocatalytic oxidation is adopted to thoroughly remove the residual organic pollutants in the wastewater, so that the effluent reaches the emission standard and even approaches to the reuse standard.
Further, the technological parameters of the electrocatalytic oxidation reaction in the step (5) are as follows: pH:6.5-8; voltage: 12-18V; current flow: 2.4-4A; electrode plate spacing: 180nm-200nm; reaction time: 20-40min, in the range of these process parameters, is favorable for thoroughly degrading the residual substances.
The ZSM-5 molecular sieve used in the invention can be recycled through subsequent regeneration treatment after adsorption saturation.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the primary oxidation flocculation tank, the sedimentation tank and the primary ozone catalytic reaction tank are additionally arranged in front of the MBR biochemical treatment system, so that the COD value of the wastewater and the toxicity of the wastewater are reduced as much as possible, and the stable and efficient operation of the subsequent MBR biochemical treatment system is ensured. The invention adds a secondary ozone catalytic reaction tank and a secondary oxidation flocculation tank at the rear end of the MBR biochemical treatment system as a two-stage advanced oxidation treatment system, and further degrades residual pollutants in the MBR produced water, so that the effluent reaches the emission standard.
The system has simple structure and stable operation, and is suitable for the prior sewage treatment plant, especially the enterprise pretreatment sewage treatment plant of fine chemical industry, and the reconstruction and extension of the centralized sewage treatment plant in the park.
Drawings
FIG. 1 is a schematic diagram showing the construction of an advanced treatment system for aromatic and heterocyclic compound wastewater according to example 1.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
The advanced treatment system for the aromatic and heterocyclic compound wastewater comprises a primary oxidation flocculation tank, a sedimentation tank, a primary ozone catalytic reaction tank, an MBR biochemical treatment system, a secondary ozone catalytic reaction tank, a secondary oxidation flocculation tank and an electrocatalytic reaction tank which are sequentially connected, wherein the MBR biochemical treatment system comprises a hydrolysis acidification tank, an A/O tank, an MBR membrane tank and an MBR water producing tank which are sequentially connected, the hydrolysis acidification tank is connected with the primary ozone catalytic reaction tank, and the MBR water producing tank is connected with the secondary ozone catalytic reaction tank.
Compared with the conventional wastewater treatment system, the invention is additionally provided with the primary oxidation flocculation tank, the sedimentation tank and the primary ozone catalytic reaction tank before the MBR biochemical treatment system, so that the COD value of the wastewater and the toxicity of the wastewater are reduced as much as possible, and the stable and efficient operation of the subsequent MBR biochemical treatment system is ensured. The invention adds a secondary ozone catalytic reaction tank and a secondary oxidation flocculation tank at the rear end of the MBR biochemical treatment system as a two-stage advanced oxidation treatment system, and further degrades residual pollutants in the MBR produced water, so that the effluent reaches the emission standard. The system is suitable for the existing sewage treatment plants, especially the enterprise pretreatment sewage treatment plants of fine chemical industry, and the reconstruction and extension of the centralized sewage treatment plants in the park.
In the invention, in order to ensure that the effluent quality reaches the standard, and no high-toxicity pollutants (which are not detected by using GC or HPLC) are in the water body, the advanced treatment system of the aromatic and heterocyclic compound wastewater also comprises an electrocatalytic reaction tank, wherein the electrocatalytic reaction tank is connected with a secondary oxidation flocculation tank. When the effluent of the secondary oxidation flocculation tank still does not reach the standard, the electrocatalytic reaction tank can be started to carry out the final deep degradation, and the organic pollutants remained in the wastewater are thoroughly removed by an electrolysis method, so that the effluent reaches the emission standard and even approaches the reuse standard.
In the invention, the electrocatalytic reaction tank contains 4-8 electrode plates, and residual substances are thoroughly degraded through the electrolysis of the multidimensional electrode.
In the invention, the primary ozone catalytic reaction tank and the secondary ozone catalytic reaction tank both contain ZSM-5 type molecular sieves, which is beneficial to improving the contact area of ozone and water, so that organic pollutants in wastewater fully react with ozone, the treatment depth of the organic wastewater is improved, and the COD value of the wastewater is reduced.
In the invention, the MBR membrane tank is also connected with the hydrolysis acidification tank and the A/O tank respectively through pipelines, and sludge generated after the MBR membrane tank treatment can flow back to the hydrolysis acidification tank for hydrolysis acidification treatment or flow back to the A/O tank for biochemical treatment respectively, so that pollutant discharge is reduced.
The invention also provides a deep treatment method of the aromatic and heterocyclic compound wastewater, which comprises the following steps:
(1) The wastewater undergoes primary oxidation reaction and flocculation precipitation in a primary oxidation reaction flocculation tank added with an oxidant and a flocculant, and enters a sedimentation tank for solid-liquid separation;
(2) The wastewater after flocculation precipitation enters a primary ozone catalytic reaction tank to carry out primary ozone catalytic reaction;
(3) The wastewater after the reaction in the step (2) enters an MBR biochemical treatment system for biochemical treatment;
(4) The wastewater after biochemical treatment is subjected to a secondary ozone catalytic reaction in a secondary ozone catalytic reaction tank, and then enters a secondary oxidation flocculation tank to carry out a secondary oxidation reaction.
Because of the stable structure of the aromatic and heterocyclic compounds, conventional advanced oxidation techniques are difficult to achieve deep thorough oxidation. The invention adopts the process of 'primary oxidation + primary ozone catalysis + hydrolytic acidification + MBR + secondary ozone catalysis + secondary oxidation', can remove high-concentration aromatic and heterocyclic compounds in the wastewater, and the effluent not only completely reaches the existing emission standard, but also approaches the reuse standard.
In the invention, the addition amount of the flocculant can be correspondingly adjusted according to the actual water quality.
In the invention, in the step (1), the addition amount of the oxidant is 0.3-0.4% of the total mass of the wastewater, the oxidant is hydrogen peroxide with the concentration of 25wt%, and the reaction time is 20-25min, thereby being beneficial to reducing the COD value of the wastewater.
In the invention, in the step (2), the ozone is added in an amount of 2-4mg O 3 COD mg, ozone mass concentration of 75% -80%, reaction time of 15-20min;
the ZSM-5 type molecular sieve is added in the first-stage ozone catalytic reaction, the adding amount of the ZSM-5 type molecular sieve is 1.2% -1.6% of the total mass of the wastewater, and the particle size of the ZSM-5 type molecular sieve is 20-30 meshes;
in the process parameter range, the COD value of the wastewater is reduced, the toxicity of the inflow water of the MBR biochemical treatment system is degraded, and the biodegradability of the inflow water is improved.
In the invention, in the step (4), the adding amount of the ozone in the secondary ozone catalytic reaction is 1.5-2.5mg O 3 COD mg, ozone mass concentration of 55% -60%, reaction time of 15-20min, ZSM-5 type molecular sieve added in the secondary ozone catalytic reaction, ZSM-5 type molecular sieve added amount of 1% -1.4% of total wastewater mass, and ZSM-5 type molecular sieve particle size of 20-30 mesh; the adding amount of the oxidant in the secondary oxidation reaction is 0.1-0.2% of the total mass of the wastewater, and the oxidant is H with the mass concentration of 16-20% 2 O 2 The reaction time is 10-15min. Within these process parameters, further degradation of the residual organics is favored.
In the invention, the advanced treatment method of the aromatic and heterocyclic compound wastewater further comprises the following steps:
(5) And (3) the wastewater subjected to the oxidation treatment in the step (4) enters an electrocatalytic reaction tank for electrocatalytic oxidation reaction.
When the effluent of the secondary oxidation flocculation tank still does not reach the standard, in order to further ensure that the quality of the effluent reaches the standard, the electrocatalytic reaction tank can be started to carry out final deep degradation, and the process of primary oxidation, primary ozone catalysis, hydrolytic acidification, MBR, secondary ozone catalysis, secondary oxidation and electrocatalytic oxidation is adopted to thoroughly remove the residual organic pollutants in the wastewater, so that the effluent reaches the emission standard and even approaches to the reuse standard.
In the invention, the technological parameters of the electrocatalytic oxidation reaction in the step (5) are as follows: pH:6.5-8; voltage: 12-18V; current flow: 2.4-4A; electrode plate spacing: 180nm-200nm; reaction time: 20-40min, in the range of these process parameters, is favorable for thoroughly degrading the residual substances.
The ZSM-5 molecular sieve used in the invention can be recycled through subsequent regeneration treatment after adsorption saturation.
Example 1
The advanced treatment system for the aromatic and heterocyclic compound wastewater in the embodiment, as shown in fig. 1, comprises a primary oxidation flocculation tank, a sedimentation tank, a primary ozone catalytic reaction tank, an MBR biochemical treatment system, a secondary ozone catalytic reaction tank, a secondary oxidation flocculation tank and an electrocatalytic reaction tank which are sequentially connected, wherein the MBR biochemical treatment system comprises a hydrolysis acidification tank, an A/O tank, an MBR membrane tank and an MBR water producing tank which are sequentially connected, the hydrolysis acidification tank is connected with the primary ozone catalytic reaction tank, and the MBR water producing tank is connected with the secondary ozone catalytic reaction tank; the primary ozone catalytic reaction tank and the secondary ozone catalytic reaction tank both contain ZSM-5 type molecular sieves.
The advanced treatment method of the aromatic and heterocyclic compound wastewater of the embodiment comprises the following steps:
(1) Firstly, the raw water of the wastewater passes through a primary oxidation reaction flocculation tank, and particulate matters such as SS (suspended solids) and the like in the wastewater and a small amount of insoluble COD are removed by adding an oxidant and a flocculant, wherein the added oxidant is H with the mass concentration of 25 percent 2 O 2 The addition amount of the oxidant is about 0.3% of the total mass of the wastewater, the reaction time t=20 min, after the reaction is completed, the wastewater enters a sedimentation tank for solid-liquid separation, and the COD= 425.8mg/L of the effluent;
(2) And (3) allowing the flocculated and precipitated wastewater to enter a first-stage ozone catalytic reaction tank for reaction, and converting part of macromolecular organic matters into micromolecular organic matters. In the primary ozone catalytic reaction, the mass concentration of ozone is 80%, and the adding amount A=2mg O 3 COD mg, reaction time t =20min; in order to improve the contact area of ozone and water, a certain amount of ZSM-5 type molecular sieve is added into an oxidation pond, the particle size is 20-30 meshes, the addition amount is about 1.2% of the total mass of wastewater, and the ZSM-5 type molecular sieve which is saturated in adsorption can be recycled through subsequent regeneration treatment; the COD of the effluent of the stage is 290.1mg/L;
(3) And (3) the wastewater treated in the step (2) enters an MBR biochemical treatment system for biochemical treatment. The MBR biochemical treatment system comprises a hydrolysis acidification tank, an A/O tank, an MBR membrane tank and an MBR water producing tank which are sequentially connected, wherein the hydrolysis acidification tank is mainly used for further converting mineralized long-chain organic matters into smaller molecules so as to facilitate biochemical treatment; the biochemical system comprising an A/O pool, an MBR membrane pool and an MBR water producing pool converts small molecular organic matters into CO under the action of microorganisms in the biochemical system 2 At the same time, further removing N and P in the wastewater; the COD=111.4 mg/L and B/C=0.41 of the produced water of the MBR membrane tank;
(4) The COD of the wastewater after biochemical treatment is obviously reduced, but pollutants which are not completely degraded exist in the wastewater, and the main components and the concentrations of the wastewater are shown in the table 1:
TABLE 1
| Name of the name | Concentration (mg/L) | Name of the name | Concentration (mg/L) |
| Benzotrifluoride (TFA) | 28.9 | M-aminotrifluorotoluene | 54.4 |
| Trichloropyridine | 46.1 | M-trifluoromethyl phenol | 36.2 |
| Dichlorobenzonitrile (DCN) | 17.5 | 2-2' bipyridines | 24.5 |
It can be seen that the toxicity of the MBR effluent remains significant, and therefore, it is necessary to continue oxidizing it. In practice, the wastewater firstly passes through a secondary ozone catalytic reaction tank to carry out a secondary ozone catalytic reaction, and then enters a secondary oxidation flocculation tank to carry out a secondary oxidation reaction. Wherein in the secondary ozone catalytic reaction, the mass concentration of ozone is 55%, and the adding amount A=1.5 mg O 3 The catalyst used is ZSM-5 type molecular sieve with the particle size of about 20-30 meshes, and the adding amount of the ZSM-5 type molecular sieve is 1.4% of the total mass of the wastewater; in the secondary oxidation reaction, the added oxidant is H with the mass concentration of 16 percent 2 O 2 The addition amount is 0.2% of the total mass of the wastewater, and the reaction time t=15 min. After two-stage advanced oxidation treatment, effluent COD=21.4 mg/L;
(5) In order to ensure that the effluent completely reaches the standard, an electrocatalytic reaction tank is added at the rear end of the two-stage advanced oxidation treatment system, the electrocatalytic reaction tank consists of 8 electrode plates, and residual substances are thoroughly degraded through the electrolysis of the multidimensional electrode. The technological parameters of the electrocatalytic reaction tank are as follows: ph=6.5; voltage u=18v; current i=4a; electrode plate spacing: 200nm; time t=40 min. After the electrocatalytic reaction was completed, the COD of the effluent was=2.17 mg/L. And none of the six organic contaminants in Table 1 above were detected. Thus, it was confirmed that the effluent reached the discharge standard.
Example 2
The advanced treatment system of aromatic and heterocyclic compound wastewater of this example was the same as that of example 1.
The advanced treatment method of the aromatic and heterocyclic compound wastewater of the embodiment comprises the following steps:
(1) Firstly, the raw water of the wastewater passes through a primary oxidation reaction flocculation tank, and particulate matters such as SS (suspended solids) and the like in the wastewater and a small amount of insoluble COD are removed by adding an oxidant and a flocculant, wherein the added oxidant is H with the mass concentration of 25 percent 2 O 2 The addition amount of the oxidant is about 0.4 percent of the total mass of the wastewater, the reaction time t=25min, after the reaction is completed, the wastewater enters a sedimentation tank for solid-liquid separation, and the COD= 420.4mg/L of the effluent;
(2) And (3) allowing the flocculated and precipitated wastewater to enter a first-stage ozone catalytic reaction tank for reaction, and converting part of macromolecular organic matters into micromolecular organic matters. The mass concentration of ozone in the primary ozone catalytic reaction is 75%, and the addition amount A=4mg O 3 COD mg, reaction time t=15 min; in order to improve the contact area of ozone and water, a certain amount of ZSM-5 type molecular sieve is added into an oxidation pond, the particle size is 20-30 meshes, the addition amount is about 1.6 percent of the total mass of wastewater, and the ZSM-5 type molecular sieve which is saturated in adsorption can be recycled through subsequent regeneration treatment; the COD of the effluent of the stage is=286.5 mg/L;
(3) And (3) the wastewater treated in the step (2) enters an MBR biochemical treatment system for biochemical treatment. The MBR biochemical treatment system comprises a hydrolysis acidification tank, an A/O tank, an MBR membrane tank and an MBR water producing tank which are sequentially connected, wherein the hydrolysis acidification tank is mainly used for further converting mineralized long-chain organic matters into smaller molecules so as to facilitate biochemical treatment; the biochemical system comprising an A/O pool, an MBR membrane pool and an MBR water producing pool converts small molecular organic matters into CO under the action of microorganisms in the biochemical system 2 At the same time, further removing N and P in the wastewater; the COD=110.2 mg/L and B/C=0.40 of the produced water of the MBR membrane tank;
(4) The COD of the wastewater after biochemical treatment is obviously reduced, but pollutants which are not completely degraded exist in the wastewater, and the main components and the concentrations of the wastewater are shown in Table 2:
TABLE 2
It can be seen that the toxicity of the MBR effluent remains significant, and therefore, it is necessary to continue oxidizing it. In practice, the wastewater firstly passes through a secondary ozone catalytic reaction tank to carry out a secondary ozone catalytic reaction, and then enters a secondary oxidation flocculation tank to carry out a secondary oxidation reaction. Wherein in the secondary ozone catalytic reaction, the mass concentration of ozone is 60%, and the adding amount A=2.5 mg O 3 The catalyst is ZSM-5 type molecular sieve, the particle size is about 20-30 meshes, and the adding amount of the ZSM-5 type molecular sieve is 1% of the total mass of the wastewater; in the secondary oxidation reaction, the added oxidant is H with the mass concentration of 20 percent 2 O 2 The addition amount is 0.1% of the total mass of the wastewater, and the reaction time t=10 min. After two-stage advanced oxidation treatment, effluent COD=17.6 mg/L;
(5) In order to ensure that the effluent completely reaches the standard, an electrocatalytic reaction tank is added at the rear end of the two-stage advanced oxidation treatment system, the electrocatalytic reaction tank consists of 4 electrode plates, and residual substances are thoroughly degraded through the electrolysis of the multidimensional electrode. The technological parameters of the electrocatalytic reaction tank are as follows: ph=8; voltage u=12v; current i=2.4A; electrode plate spacing: 180nm; time t=20 min. After the electrocatalytic reaction was completed, the COD of the effluent was=2.02 mg/L. And none of the six organic contaminants in table 2 above were detected. Thus, it was confirmed that the effluent reached the discharge standard.
In other embodiments, if the effluent after the two-stage advanced oxidation treatment in the step (4) has reached the emission standard, the electrocatalytic oxidation reaction in the step (5) is not needed, so that the energy consumption of the system is reduced.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (4)
1. The advanced treatment method of the aromatic and heterocyclic compound wastewater is characterized by comprising an advanced treatment system of the aromatic and heterocyclic compound wastewater, wherein the advanced treatment system of the aromatic and heterocyclic compound wastewater comprises a primary oxidation flocculation tank, a sedimentation tank, a primary ozone catalytic reaction tank, an MBR biochemical treatment system, a secondary ozone catalytic reaction tank, a secondary oxidation flocculation tank and an electrocatalytic reaction tank which are sequentially connected, the MBR biochemical treatment system comprises a hydrolysis acidification tank, an A/O tank, an MBR membrane tank and an MBR water producing tank which are sequentially connected, the hydrolysis acidification tank is connected with the primary ozone catalytic reaction tank, and the MBR water producing tank is connected with the secondary ozone catalytic reaction tank;
the advanced treatment method of the aromatic and heterocyclic compound wastewater comprises the following steps:
(1) The wastewater undergoes primary oxidation reaction and flocculation precipitation in a primary oxidation reaction flocculation tank added with an oxidant and a flocculant, and enters a sedimentation tank for solid-liquid separation;
(2) The wastewater after flocculation precipitation enters a primary ozone catalytic reaction tank to carry out primary ozone catalytic reaction;
(3) The wastewater after the reaction in the step (2) enters an MBR biochemical treatment system for biochemical treatment;
(4) The wastewater after biochemical treatment is subjected to secondary ozone catalytic reaction in a secondary ozone catalytic reaction tank, and then enters a secondary oxidation flocculation tank to carry out secondary oxidation reaction;
(5) The wastewater subjected to the oxidation treatment in the step (4) enters an electrocatalytic reaction tank for electrocatalytic oxidation reaction;
in the step (1), the adding amount of the oxidant is 0.3-0.4% of the total mass of the wastewater, the oxidant is hydrogen peroxide with the mass concentration of 25%, and the reaction time is 20-25min;
in the step (2), the ozone is added in an amount of 2-4mg O 3 CODmg, ozone mass concentration is 75% -80%, reaction time is 15-20min;
the ZSM-5 type molecular sieve is added in the first-stage ozone catalytic reaction, the adding amount of the ZSM-5 type molecular sieve is 1.2% -1.6% of the total mass of the wastewater, and the particle size of the ZSM-5 type molecular sieve is 20-30 meshes; in the step (4), the ozone adding amount in the secondary ozone catalytic reaction is 1.5-2.5mg O 3 COD mg, ozone mass concentration of 55% -60%, reaction time of 15-20min;
ZSM-5 type molecular sieve is added in the secondary ozone catalytic reaction, the adding amount of the ZSM-5 type molecular sieve is 1% -1.4% of the total mass of the wastewater, and the particle size of the ZSM-5 type molecular sieve is 20-30 meshes;
the adding amount of the oxidant in the secondary oxidation reaction is 0.1-0.2% of the total mass of the wastewater, and the oxidant is H with the concentration of 16-20% 2 O 2 The reaction time is 10-15min.
2. The method for advanced treatment of aromatic and heterocyclic compound wastewater according to claim 1, wherein the electrocatalytic reaction cell comprises 4-8 electrode plates.
3. The method for advanced treatment of aromatic and heterocyclic compound wastewater according to claim 1, wherein the primary ozone catalytic reaction tank and the secondary ozone catalytic reaction tank each contain ZSM-5 type molecular sieves.
4. The advanced treatment method for aromatic and heterocyclic compound wastewater according to claim 1, wherein the technological parameters of the electrocatalytic oxidation reaction in step (5) are as follows: pH:6.5-8; voltage: 12-18V; current flow: 2.4-4A; electrode plate spacing: 180nm-200nm; reaction time: 20-40 min.
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